Alkylation process



Patented Dct. 21,1941

. summon rnoonss Seaver A. Ballard and John Anderson, Berkeley, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation'of Delaware No Drawing. Application March 1, 1940,

, Serial No. 321,803

11 Claims. (Cl. 196-10) This invention relates to the alkylation of organic compounds by reaction with olefines or sulfate esters in the presence of inorganic acids of sulfur capable of catalyzing such alkylation.- The invention is more particularly directed to the use of novel alkylation catalyst mixtures in such reactions.

An important object of the invention is to increase the effective life of inorganic sulfur acid alkylation catalysts such as sulfuric, chlorsulfonic, fiuorsulfonic and like acids. Another object is to reduce the cost of alkylating organic compounds by reducing the catalyst consumption and increasing the efiiciency of the reaction. Although the invention is not limited thereto it is particularl applicable to the production of motor fuels and a special object is to produce hydrocarbons of high antiknock value and to obtain high yields of highly branched chain paraflins boiling in the gasoline range from isoparaifins and olefines. Still other objects and advantages of the invention will be apparent from the following description.

The alkylation of aromatic and analogous heterccyclic compounds by olefines and alkyl sulfates using sulfuric acid as thealkylation catalyst-has long been known. A particularly advantageous method of producing alkylated phenolic bodies is described, for example, in United States Patent 2,051,473. The alkylation of is'oparafiins in thepresence of sulfuric acid is a more recent development which is claimed in copending applications Serial No. 150,544, filed June 26, 1937, Serial No. 276,062, filed May 27, 1939 and Serial No. 305,498, filedNovember 21,

1939. Other alkylation processes using sulfuric acid as the catalyst are described, for example,

in United States Patents 2,001,909 and 2,006,695.

While such alkylations are known to be essentially catalytic reactions, the sulphuric acid catalysts have been found in practice to lose their effectiveness in promoting alkylation after relatively short periods of .use. TIhe regeneration of such spent sulfuric acid requires dilution, decomposition of absorbed impurities, and reconcentration and involves losses of acid and operating expenses which make regenerated acid very costly. Such regeneration is consequently to be avoided as much as possible. This is made possible by the process of the invention which greatly extends the time which sulfur acid alkylation catalysts may be used without losing their effectiveness.

fully known and probably varies with the nature of the materials used and the conditions of alkylation employed. Thus, for example, in alkylating isoparafllns such as isobutane and isopentane the consumption of sulfuric acid is much greater under optimum alkylating conditions when propylene is used as the alkylating agent then when beta-butylene is employed. In fact the sulfuric acid requirements for alkylating isoparaflins with propylene have heretofore been so great as to limit commercial application of V thereof. The high cost, short life of regenerating halo-sulfonic acid alkylation cat The cause of the loss of effectiveness of alkylation catalysts such as sulfuric acid is not the reaction. The application of the process of the invention to this reaction will therefore be emphasized in the following discussion because of its commercial importance. It is to be understood, however, that the invention is not limited to this illustrative example but that similar advantages and improvements may be obtained in other alkylation reactions carried out with olefines and/or alkyl sulfates in the presence of sulfuric and halo-sulfonic acids or mixtures and difficulty alysts such as chlorand fluorsulfonic acids makes the present process particularly valuable where alkylation with such catalysts is used. Typical of other alkylation reactions in which the process of the invention gives improved results are the alkylation of benzene, toluene, naphthalane, phenol, cresols and naphthol.

In accordance with the invention many of the disadvantages of the former sulfuric acid alkylation processes are successfully overcome by substituting for concentrated sulfuric, chlorsulionic and fluorsulfonic acids a novel alkylation catalyst, namely, a mixture of such acidwith a hydrogen halide. From an economic standpoint there are advantages in using mixtures of concentrated sulfuric acid and hydrogen chloride because of the low cost of these acids but mixtures of sulfuric acid with hydrogen bromide or kylation catalysts and hydrogen halides may be carried out under the same reaction conditions found suitable with the corresponding sulfur acid alone. 7 Thus, for example, in alkylating isoparaflins such as isobutane and isopentane with olefines temperatures between about 0 and 50 C; ma be used with mixtures of sulfuric acidv of mixtures is between about alkylation about 90% to 110% concentration (on a hydrocarbon free basis) and hydrochloric acid while lower temperatures of the order of about 80' to about 20 C. are preferable with similar mixtures in which chlorsulfonic acid is used in plac of sulfuric acid. The preferred range of temperatures for fluorsulfonic acid hydrochloric acid 7 -40 and 25' 0. although higher temperatures, for example up to about 100 C. may be used.

For the preparation of mono-alkyl derivatives it is desirable to employ at least a small molecular excess of the compound being alkylated compared with the amount of oleflne used. Where isoparaflins are'being alkylated it is advantageous to use a substantial excess of iso paraflin to oleflne. with sulfuric acid catalysts ratios of at least 3 mols of isoparaflin to one of oleflne in the feed are desirable while ratios of up to 5 or 6 to 1 are preferred and best results are usually obtained by carrying out the alkylation under conditions such that ratios of 10 to 30 mols or more of isoparaflin per' moi of oleflne are present in the reaction mixture. While it is also advantageous to employ an excess of isoparaflin'to olefine, preferably at least two mols of isoparaflin per mol of oleflne, when using the halogen acid containing alkylation acid mixtures of the invention, it is possible to employ lower ratios than have been found necessary for the best results with sulfuric acid alone.

This is of practical advantage because it reduces the cost of supervision required in former procedures where rigid control of the reaction is necessary in order to maintain the ratio of isoparafiin to olefine constant in spite of fluctuations in the composition of the feed. It has the further. advantage of making possible a reduction in the amount of unreacted isoparailln which must be recovered from the alkylation product and recycled to the reaction, an operation usually requiring redistillation to separate undesirable diluents such as the corresponding normal paraflln. Y

The process may be carried out with the reactants in the gaseous state but more preferably reaction under conditions at which at least the compound being alkylated is in the liquid phase are used and most preferably reaction conditions which insure the presence'of all reactants at least partially in the liquid phase are employed. To the latter end it is usually advantageous to operate under superatmospheric pressure when using low boiling reactants. In liquid phase operation it is usually desirable to employ a volume of catalyst phase at least equal to about 20%, and more preferably about 40% to about 150%, of the volume of hydrocarbons used.

While quite short contact times of the order of one-half to five minutes may be used particularly where reaction in the gas phase is being carried out, contact times of hydrocarbon with sulfuric acid-hydrochloric acid mixtures of the order of 15 to 60 minutes or more such as are.

more conveniently achieved by liquid phase operation are preferred for the alkylation of isopar- 'aflins with oleflnes or -alkyl sulfates. The best reaction time to use in any given case will-depend upon the compound being alkylated, the agent used, the particular combination of sulfur acid allwlation catalyst and hydrogen halide chosen and the reaction conditions employed.

Batch, intermittent or continuous methods of which may vary with the method of operation chosen, may be used-for insuring the presence of the desired hydrogen halide in the reaction mixture. Thus hydrogen chloride, preferably anhydrous, may be added with the hydrocarbon feed to the reactor to compensate for that withdrawn with the product or liquid hydrogen chloride either anhydrous or dissolved in water or other suitable solvent may be added to catalyst acid directly, care being taken of course, to avoid dilution of the sulfuric or like acid to concentrations below those suitable for the desired alkylation.

One simple method of carrying out the process of the invention is to bubble isoparaflin and oleflne containing gases saturated with hydrogen chloride through a preferably mechanically agitated body of sulfuric acid alkylation catalyst. Jets or other distributing means may be employed to inject the liquid and/or gaseous hydrocarbons and thus provide the desired agitation. Towers, provided with trays or perforated plates or packing material over which the mixture of sulfuric and hydrochloric or like acids and hydrocarbon is allowed to flow, may also be used. In some cases it may be desirable to have counter-current flow between a mixture of the compound being alkylated in the liquid phase and sulfuric acid for example on the one hand and the oleilne in the gaseous state and hydrogen chloride on the other. Most preferably, however, oleflnes are reacted with isoparafllns by feeding the oleflne or the corresponding dialkyl sulfates or suitable absorption products of oleflnes in sulfuric acid of alkylation strength and hydrogen chloride or the like, preferably with a molecular excess of the isoparaflln based on the olefine, into a circulating mass of reacted mixture comprising dispersed sulfuric acid whereby operation may be used. Different procedures the reaction is effected with a higher ratio of isoparaflln to oleflne than is present in the feed as described and claimed in copending application Serial No. 245,714, flied December 14, 1938.

The amount of hydrogen halide which may be used may vary widely; As little as 0.25% of hydrogen chloride based on the hydrocarbons used is effective in increasing the life of sulfuric acid used foralkylating isobutane with propylene.

'Amounts greatly in excess of a molecular equiv- 4 alent based on the olefine and/or alkyl sulfate present are of no advantage. on the whole only relatively small amounts of hydrogen chloride, or other suitable hydrogen halide are required since there is no substantial loss in the process when care is taken to recover and recycle any halides which are withdrawn with .the product.

A part of the hydrogen halide may be present in the withdrawn reacted mixture as alkyl halides which are preferably returned to the reaction along with any free hydrogen halide present. In this way consumption of hydrogen halide is prevented since the accumulation of alkyl halides in the system is prevented either through reaction or the mass action effect of the recycled alk'yl halides.

The following example shows the advantages of the invention and illustrates one suitable method of applying its principles.

Example I Hydrogen chloride wasblended with the feed to a continuous alkylation unit of the turbomixer type provided with a cooling coil and inlet lines for the hydrocarbon reactants and returned acid catalyst and a draw-oi! line leading assume to a stratifier from which upper hydrocarbon.

phase was continuously removed while the lower acid phase was taken ofl by the acid return line. The reactants were fed in under a pressure ofv about 250 to 300 lbs/sq. in.'and hydrocarbon phase was withdrawn from the separator at the same rate. The withdrawn hydrocarbon phase was distilled to separate alkylation products from the hydrogen chloride. unreacted hydrocarbons and chlorinated hydrocarbons present therewith and the various products were measured and analyzed. Instarting up 98% sulfuric. acid mixed with isobutane was charged to the reactor before the feed was admitted. The operating conditions and results were as follows:

Composition of the feed (wt. per cent):

- Per cent Propylene 7.0 Propane 18.3 n-Butane 3.9 Isobutane -a 70.2 Hydrogen chloride 0.6

Feed rate 1.55-1.81 volumes/hour/volume of reaction space.

Average contact time of hydrocarbon with acid-20 min.

Mol ratio of isobutane to olefine in feed- 7.3 to 1 Volume ratio of acid to hydrocarbon-+0.7 to 1 Reaction temperature, 30 C.

Weight per cent of product based on oleiine feed-163.

Octane rating of fraction boiling 45-l50 C.-89.0. Volumes of product per volume of acid used-6.32.

By returning the fraction boiling between 23 and 45 0., consisting substantially of isopropyl chloride, to the reactor the yield of substantially chlorine free alkylation products boiling between 45 and 150 C. could be raised to about 175%. In a run carried out under exactly "the same conditions except that no hydrogen chloride was used the yield (weight percent of products boiling above 23 0., based on the propylene fed) was only 144% and only 5.46 volumes were obtained per volume of acid used.

Improved acid life also is obtained when other oleflnes are used in place of propylene as abovedescribed, particularly normal and isobutylenes, trimethyl ethylene and isomeric amylenes, and cyclohexene. The process may also be employed with other olefines such as the higher normally liquid oleflnes of cracked gasoline or fractions thereof. Instead of the olefinestheir polymerization products such as diand jtri-isobutylenes. the interpolymers of different oleflnes such as are described in United States Patents 2,174,247

' and 2,181,640 and the like'may be used. Particularly suitable feed stock for the process is the residual hydrocarbon obtained in the process of the latter patent. Such hydrocarbon may be used with or without separation of the polymers formed in the process. Instead of oleflnes alkyl of oleilnes' or alcohols with sulfuric acid may be used. Thus monoand/or di-ethyl, propyl, isopropyl. isobutyl and like sulfates may be used as the alkylating agent in accordance with the process of the invention.

Instead of using the process of the invention as a substitute for prior sulfuric acid and like mixer with an equal volume of isobutane. An-

it may be used in conjuncfor example, sulfuric acid alkylation processes, tion therewith. Th

.which has been used in such an alkylation process may be continuously or intermittently conducted to another reaction stage in which it is contacted with a mixture of isoparaflin and hydrogen chloride whereby alkylation of the isoparainn by alkyl esters present in the acid is effected and the efl'ectiveness of the acid as an alkylation catalyst is increased so that it may advantageously be returned to the first alkylation stage for the conversion of more isoparaflin and olefln'e. The effectiveness of such a method of treating alkylation acid is illustrated by the .iollowing example.

Example II In the same apparatus used 'in Example I isobutane was reacted with propylene in the presencev of sulfuric acid alone under the same conditions except that a temperature of 40 C. was used. The initial concentration of the acid was 98.1% but the acid phase withdrawn after the production of 4.25 volumes of products per volume of acid had a titratable acidity of only This acid was charged to a reaction hydrous hydrogen chloride was added to raise the pressure to 100 lbs. The mixture was stirred for 3 hours at 20 C. while additional hydrogen chloride was added intermittently to maintain the pressure. By this procedure alkylation of the isobutane took place and the titratable acidity of the acid was increased to 79% H2804. An appreciable amount of isopropyl chloride was also formed. Return of this product to the reactor with or without separation of the. unreacted isobutane could be used to increase the yield of alkylation products obtained. By'returning the treated acid to the olefine reaction stage it could be again made to serve as an alkylation catalyst, although best results are obtained by using it in admixture with fresh acid.

In a similar test run on the alkylation of isobutane with a butane-butylene mixture containlng beta-butylene as the principal olefine, ob-

' was likewise materially increased and alkylation sulfates such as may be obtained by treatment tained as unreacted hydrocarbon from the treatment of a C4 fraction of. cracked petroleum with hot sulfuric acid to polymerize isoand second ary butylenes, the acidity of the alkylation acid products were obtained. In this case some secondary butyl chloride was also formed.

'It will be seen that the process of the inven tion offers many advantages particularly in in-' creasing the effective life of sulfur acid alkylation catalysts. Even greater increases in the life of such catalysts may be obtained by combining the process of the invention with pretreatment of the feed to the alkylation unit to remove catalyst poisons as described and claimed in co pending application Serial No. 281,882, filed June 29, 1939.

The invention offers special advantages in the treatment of petroleum fractions or products and is especially'useful in the manufacture of premium motor fuels from petroleum cracking products. However, starting materials derived I by dehydrogenation, for example, as described mums momma States Patents 2,182,431 and 2,184,235,

and/or isomerization of parafiins asdisclosedin French Patent 823,595; for example. may also be used. It will thus be clear capable of wide materials which may be 'alkylated oletines and sulfate esters which alkylating agents. The operatthe invention is respect to the as well as the may be used as that the process of variation .with

ing procedure adopted may also be varied. Thus while the separation and return of'hydrogenhalide and alkyl halide to the alkylation process has been described in the illustrative examples,

the actual segregation of these components of the reaction mixture separation of the des ticularly when it is halides formed, and

ponents, i. e., unreacted terial, hydrogen halide or without any diluents such as normal parafllns is not necessary and mere ired reaction product, parhigher boiling than the alkyl return' of all other comalkylatable starting maand alkyl halide, with or hydrogen or other gases, to the alkylation may oifer advanta es. Also where desirable the alkyl halide may be recovered as a valuable by-Product and only the unalkylated two-stage alkylation process recycled. In the described, the entire starting material reaction mixture from the reaction with used catalyst acid may be fed to the stage in which the oleflne is being fed thus effecting both stages of the reaction in the presence of hydrogen halide from the final reaction product is or without unreacted atable compounding tors or to only the which after separation returned, with isoparaflln or other alkylbeingused, to both reacused catalyst acid reactor. Alternatively alkylation products alone or together with any alkyl halides formed may be separated from the used catalyst acid reaction mixture prior to'feeding remaining components to the other reaction sirable to operate the reaction stages ferent conditions and with out the reaction temperature than more active catalyst mote more vigorous than two reaction stage. Also it may be deunder difparticularly to carrying used catalyst at a higher used in the stage where is employed in order to proreaction. Obviously, more stages may be used and oleflne or sulfate ester alkylating agent may be supplied to any 01" all of the stages, instead ofto only one stage as described. As still other variations may be made in the process it will be understood that the invention is not limited to the details disclosed nor by any theory suggested in explanation of the improved results obtained but only by the accompanying claims.

We claim as our invention:

1. In a process for producing gasoline motor fuel from normally, step gaseous hydrocarbons, the

of reacting isobutane with a normally gaseous olefine of at least three carbon atoms per molecule in the presence of a catalyst consist- 6o ing predominantly of a mixture of sulfuric and hydrochloric acids.

2. In a process for a normally gaseous oleflne of at bon atoms .per molecule, the step of treating a producing motor fuel from least three carliquid mixture comprising said oleflne and a substantial molecular excess mixture of sulfuric.

of isobutane with a and hydrochloric acids in substantial proportions.

3. In the alkylation of isobutane with a normally gaseous olefine of atoms per molecule, comprises reacting the line in the presence mixture of sulfuric a at least three carbon the improvement which isobutane with said oleoi a catalyst comprising a cid with a hydrogen halide which comprises eifecting presence of a substantial amount of hydrogen chloride.

5. A process for producing substantially saturated normally liquid hydrocarbons which comprises reacting a mixture consisting of at least one parafllnic hydrocarbon containing at least one tertiary carbon atom per molecule and an oleflnic hydrocarbon at a temperature between -20 and +40 C. in the presence of a mixture of sulfuric and hydrochloric acids.

6-. In the alkylationof an isoparaflin by reaction with an alkylating agent of the class consisting of oleflnes and alkyl sulfuric esters in the presence of sulfuric acid, the improvement which comprises adding hydrogen chloride to the feed prior to contacting it withthe sulfuric acid.

7. In the alkylation of an aromatic compound by reaction with an alkylating agent of the class consisting of oleilnes and alkyl sulfuric esters in the presence of sulfuric acid, the improvement which comprises adding a hydrogen halide of the class consisting of hydrogen chloride and hydrogen bromide to the reaction mixture.

8. In a process for alkylating an organic compound in which a hydrogen atom can be substi- "tuted by an alkyl group by-reaction with-an alkylating agent of,

the class consisting of oleflnes and alkyl sulfate esters in the presence of sulfuric acid, the improvement which comprises contacting said reactants with said acid in the presence of a hydrogen halide of the class consisting of hydrogen chloride and hydrogen bro- 9. In a process for alkylating an organic compound in which a hydrogen atom can be substituted by an alkyl group by reaction with an alkylating agent of the class consisting of oleilnes and alkyl sulfate esters in the presence of sulfuric acid, the improvement which contacting said reactants with said acid in the presence of a hydrogen halide of the class consisting of hydrogen'chloride and hydrogen bromide, substantially separating a halogen compound from the alkylation product and returnving at least a part of said separated halogen of sulfuric acid, the improvement which com-- prises contacting acid from said reaction which has lost at least a part of its capacity for catalyzing said reaction with said alkylatable organic compound in the presence of hydrogen chloride.

11. In a process for alkylating an organic 5 compound in which a hydrogen atom can be substituted by an alkyl group by reaction in the presence of a sulfur acid alkylation catalyst with an alkylating agent of the class consisting of oletines and alkyl sulfate esters, the improvement which comprises contacting said reactants with said acid in the presence of a hydrogen halide of the class consisting of hydrogen chlo-' ride and hydrogen bromide.

SEAVER A. BALLARD. JOHN ANDERSON.

comprises 

